TWI608062B - Resin composition, semiconductor device using said resin composition, and method of producing semiconductor device - Google Patents

Description

Resin composition, semiconductor device using the same, and method of manufacturing semiconductor device

The present invention relates to a resin composition, a semiconductor device using the same, and a method of manufacturing a semiconductor device.

The present application claims priority based on Japanese Patent Application No. 2011-121386, filed on Jan. 31,,,,,,,,

In a semiconductor device, a semiconductor element is fixed to a substrate such as a lead frame, a heat sink, or a substrate with an adhesive layer interposed therebetween. Such an adhesive layer is required to have conductivity and thermal conductivity in addition to adhesion, and is known to be formed by a paste-like resin composition containing metal particles. For example, in Patent Documents 1 and 2, it is described that the adhesive layer is formed of a paste-like resin composition containing silver particles.

[Previous Technical Literature] [Patent Document]

Patent Document 1 Japanese Patent Laid-Open No. Hei 5-89721

Patent Document 2 Japanese Patent Laid-Open No. 7-118616

In order to obtain desired conductivity and thermal conductivity, such a resin composition contains a large amount of metal particles. If a large amount of metal particles are contained, the viscosity of the resin composition is increased, and coating becomes difficult, so it is necessary to lower the viscosity of the resin to be used.

However, since the specific gravity of the metal particles is larger than that of the resin component, if the viscosity of the resin is lowered, the sedimentation speed of the metal particles during use or during placement becomes faster. Therefore, the resin composition containing a large amount of metal particles is unstable, and the viscosity changes greatly with time and is difficult to use.

On the other hand, when a semiconductor element having a small wafer width such as a light-emitting diode element or a semiconductor laser element is adhered to a substrate, it is necessary to apply a small amount of the resin composition on the substrate with a precise thickness, so that the pressure is applied. The resin composition is applied by printing or dispensing with a very thin needle tube.

When the resin composition is stretched over a glass plate or the like and then placed in a thin shape, the viscosity changes greatly, and thus the stamping may not be smoothly performed. Further, in the above-mentioned resin composition, the viscosity in the extremely thin needle tube is increased to cause clogging in the needle tube, and there is a possibility that the resin composition cannot be discharged smoothly. Therefore, a resin composition containing a large amount of metal particles is particularly unsuitable for adhering a semiconductor element having a small wafer width to a substrate.

On the other hand, in the resin composition in which silver particles are dispersed in the thermosetting resin, spherical cerium oxide having an average particle diameter of 0.1 to 1.0 μm is contained, and sedimentation of the silver particles can be suppressed. However, since the spherical cerium oxide is insulative, there is a case where the conductivity is deteriorated if it is contained in the adhesive layer. In addition, in the same document, it is described that the particle size of the silver particles is reduced, and the sedimentation suppressing effect of the metal particles is suppressed to some extent. However, the paste becomes highly viscous and the coating workability is deteriorated.

The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition excellent in workability.

When the inventors of the present invention concentrated on the mechanism of the viscosity change of the resin composition with time, it was found that the metal particles having a particle diameter exceeding 10 μm were the cause, and the present invention was completed.

That is, according to the present invention, a resin composition for adhering a paste-like resin composition of a semiconductor element and a substrate, comprising: a thermosetting resin; and metal particles; wherein the metal particles are provided The volume-based particle size distribution measured by a flow particle image analyzer is d ₉₅ based on 10 μm or less.

The d ₉₅ of the metal particles contained in the resin composition is 10 μm or less. In other words, by making the volume ratio of the metal particles having a particle diameter of more than 10 μm less than 5%, it is difficult for the metal particles to settle. Therefore, the viscosity of the resin composition of the present invention changes little with time, and the workability is excellent.

Further, according to the present invention, there is provided a semiconductor device comprising: the substrate; the semiconductor element; and an adhesive layer interposed between the substrate and the semiconductor element for adhering the both, wherein the The adhesive layer is formed using the above resin composition.

Further, according to the present invention, there is provided a method of manufacturing a semiconductor device, comprising: applying the resin composition to at least one of the semiconductor element or the substrate; And a step of forming the adhesive layer by pressure-bonding the semiconductor element and the substrate, and then heating and hardening.

According to the present invention, it is possible to provide a resin composition excellent in workability.

[Best Practice for Carrying Out the Invention]

Hereinafter, embodiments of the present invention will be described.

(resin composition)

The paste-like resin composition of the present embodiment is used for adhering a semiconductor element and a substrate, and contains (A) a thermosetting resin and (B) a metal particle. Further, (b) the volume-based particle size distribution of the metal particles measured by the flow field type particle image analyzer has a d ₉₅ of 10 μm or less. In other words, the volume ratio of the metal particles having a particle diameter of more than 10 μm is less than 5%.

Here, d ₉₅ represents a particle diameter in which the cumulative volume ratio is 95%.

When the d _{95 of the} metal particles (B) contained in the resin composition is 10 μm or less, the dispersibility of the (B) metal particles in the resin composition is good, and sedimentation is less likely to occur. Therefore, the resin composition of the present embodiment has a small change in viscosity and is excellent in workability.

Further, when a semiconductor element having a small wafer width such as a light-emitting diode element or a semiconductor laser element is adhered to a substrate, it is necessary to accurately measure a small amount of the resin composition by embossing or using a very thin needle tube. Apply to the substrate. The resin composition used for imprinting is required to have a small change in viscosity on a glass plate or the like, and it is required that the resin composition used in the point of using a very thin needle tube does not cause clogging of the resin composition in the needle tube.

The resin composition of the present embodiment has a small change in viscosity and excellent workability, and can accurately apply a small amount of the resin composition to the substrate by imprinting or by using a very thin needle tube. Therefore, although it is not particularly limited, it is suitable to adhere a semiconductor element having a small wafer width such as a light-emitting diode element or a semiconductor laser element to a substrate.

(thermosetting resin)

(A) A thermosetting resin is a general thermosetting resin which forms a three-dimensional mesh structure by heating. The (A) thermosetting resin is not particularly limited, but is preferably a material which forms a liquid resin composition, and is preferably a liquid at room temperature. shape. For example, a cyanate resin, an epoxy resin, a resin having two or more radical polymerizable carbon-carbon double bonds in one molecule, a maleimide resin, or the like can be used.

(A) The cyanate resin of the thermosetting resin is a compound having a -NCO group in the molecule, which is a structure in which a -NCO group is reacted to form a three-dimensional network structure by heating, and the hardened resin and the hardened polyfunctional cyanate are cured. a compound or a low molecular weight polymer thereof. (C) The cyanate resin of the thermosetting resin is not particularly limited, and examples thereof include 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, and 1,3,5-tricyanoxine. Benzobenzene, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, 1,6-dicyanooxynaphthalene, 1,8-dicyanooxynaphthalene, 2,6-dicyandi Naphthalene, 2,7-dicyanooxynaphthalene, 1,3,6-tricyanooxynaphthalene, 4,4'-dicyanoxybiphenyl, bis(4-cyanooxyphenyl)methane, double (3,5-Dimethyl-4-cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)propane, 2,2-bis(3,5-dibromo-4- Cyanooxyphenyl)propane, bis(4-cyanooxyphenyl)ether, bis(4-cyanooxyphenyl) sulfide, bis(4-cyanooxyphenyl)fluorene, ginseng (4-cyano a reaction product such as oxyphenyl)phosphite or bis(cyanooxyphenyl)phosphate, and a cyanate ester obtained by reacting with a phenol resin and an amine halide, etc., A prepolymer of a triazine ring formed by the trimerization of cyanate groups of these polyfunctional cyanate resins. The prepolymer can be obtained by polymerizing the above polyfunctional cyanate resin monomer with a base such as an acid such as mineral acid or Lewis acid, a sodium alkoxide or a tertiary amine, or a salt such as sodium carbonate. .

(A) The hardening accelerator of the cyanate resin of the thermosetting resin can be exemplified by a general public. For example, an organic metal complex such as zinc octoate, tin octylate, cobalt naphthenate, zinc naphthenate, iron acetonitrile, metal salts such as aluminum chloride, tin chloride, zinc chloride, triethylamine, and dimethyl An amine such as a benzylamine, but is not limited thereto. These hardening accelerators may be used alone or in combination of two or more.

Further, a cyanate resin, an epoxy resin, an oxetane resin, a resin having two or more radically polymerizable carbon-carbon double bonds in one molecule, and a maleimide resin can also be used in combination. Other resins.

(A) The epoxy resin of the thermosetting resin is a compound having one or more glycidyl groups in the molecule, and is a compound which is cured by a glycidyl group by heating to form a three-dimensional network structure. (A) The epoxy resin of the thermosetting resin is preferably one containing two or more glycidyl groups in one molecule, because even if only one glycidyl group-containing compound is reacted, it is not sufficient to exhibit sufficient The nature of the hardened material.

(A) Among the epoxy resins of the thermosetting resin, a compound containing two or more glycidyl groups per molecule may be a bisphenol compound such as bisphenol A, bisphenol F or biphenol, or a derivative thereof. Hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol; diol having alicyclic structure such as cyclohexanediol, cyclohexanedimethanol or cyclohexane diethanol or derivatives thereof; An epoxidized bifunctional such as an aliphatic diol such as a diol, octanediol, decanediol or decanediol or a derivative thereof; a trifunctional structure having a trishydroxyphenylmethane skeleton or an aminophenol skeleton; An epoxidized polyfunctional substance such as a phenol resin, a cresol resin, a phenol aralkyl resin, a biphenyl aralkyl resin, or a naphthol aralkyl resin, but is not limited thereto. Further, since the resin composition is preferably liquid at room temperature, the epoxy resin of the (A) thermosetting resin is preferably liquid alone or in a mixture at room temperature. A method of epoxidizing a diol or a derivative thereof by a method in which two hydroxyl groups of a diol or a derivative thereof are reacted with epichlorohydrin to convert it into a glycidyl ether, and epoxidation is carried out. In addition, the same applies to the trifunctional or higher substances.

Reactive diluents can also be used as is conventional. Examples of the reactive diluent include phenyl glycidyl ether and tertiary butyl phenyl glycidyl ether. A monofunctional aromatic glycidyl ether such as a cresyl glycidyl ether or an aliphatic glycidyl ether.

In the case of using the epoxy resin of the (A) thermosetting resin as the (A) thermosetting resin, the resin composition of the present embodiment contains a curing agent in order to cure the epoxy resin.

Examples of the curing agent of the epoxy resin of the (A) thermosetting resin include an aliphatic amine, an aromatic amine, a dicyandiamide, a diterpene compound, an acid anhydride, and a phenol resin.

Examples of the diterpene compound of the hardener of the (A) thermosetting resin epoxy resin include dioxane adipate, dinonanoate, diammonium isophthalate, and p-hydroxybenzoic acid. Diterpenoid carboxylic acid diterpene and the like.

Examples of the acid anhydride of the hardener of the epoxy resin include phthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, and tetramethylene tetrahydroortho Phthalic anhydride, dodecene succinic anhydride, maleic anhydride, and the like.

The phenol resin which is a hardener of the epoxy resin of (A) thermosetting resin is a compound which has two or more phenolic hydroxyl groups in one molecule. In the case of a compound having one phenolic hydroxyl group in one molecule, since it cannot be used as a crosslinked structure, the properties of the cured product are poor and cannot be used. In addition, the phenol resin which is a curing agent of the epoxy resin of the (A) thermosetting resin may be two or more phenolic hydroxyl groups in one molecule, and preferably two or more in one molecule. The following phenolic hydroxyl groups are more preferably those having 2 or 3 phenolic hydroxyl groups in one molecule. In many cases, the molecular weight becomes too large, and the viscosity of the resin composition becomes too high, which is not preferable. Such a compound may, for example, be bisphenol F, bisphenol A, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, dihydroxybiphenyl ether or dihydroxy bis Phenyl ketone, tetramethylbiphenol, Bisphenols such as ethylene bisphenol, methyl ethylene bis(methyl phenol), cyclohexylene bisphenol, biphenol, and derivatives thereof, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane A trinuclear or trinuclear compound, a derivative thereof, and the like, and a compound obtained by reacting a phenol such as phenol or cresol with formaldehyde.

(A) The curing accelerator of the epoxy resin of the thermosetting resin may, for example, be an imidazole, a salt of triphenylphosphine or tetraphenylphosphonium, an amine compound such as azobiscycloundecene or a salt thereof. Preferred are 2-methylimidazole, 2-ethylimidazole-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 Imidazole compound such as phenyl-4,5-dimethylolimidazole, 2-C ₁₁ H ₂₃ -imidazole, adduct of 2-methylimidazole and 2,4-diamino-6-vinyltriazine . Among them, an imidazole compound having a melting point of 180 ° C or higher is particularly preferred. Further, the epoxy resin is also preferably used in combination with a cyanate resin, a resin having two or more radical polymerizable carbon-carbon double bonds in one molecule, and a maleimide resin.

(A) A thermosetting resin having two or more radically polymerizable carbon-carbon double bonds in one molecule, a compound having a carbon-carbon double bond in a molecule, formed by a carbon-carbon double bond 3 dimensional mesh structure, and hardened resin.

In the resin of the (A) thermosetting resin having two or more radically polymerizable carbon-carbon double bonds in one molecule, the molecular weight of (A) is preferably from 500 to 50,000. In the case where it is smaller than the above range, the modulus of elasticity of the adhesive layer may become too high, and in the case where it is larger than the above range, the viscosity of the resin composition may become too high.

The resin preferably having two or more radical polymerizable carbon-carbon double bonds in one molecule is exemplified below, but is not limited thereto.

a compound having two or more propylene groups in one molecule, preferably a polyether, a polyester, a polycarbonate, or a poly(methyl) having a molecular weight of 500 or more and 50,000 or less. A acrylate, a polybutadiene, or a compound having two or more propylene groups in one molecule of a butadiene-acrylonitrile copolymer.

The polyether is preferably an organic group having a carbon number of 3 to 6 which is repeated with an ether bond, and is preferably one which does not contain an aromatic ring. In the case of containing an aromatic ring, a compound having two or more propylene groups in one molecule becomes solid or highly viscous, and in the case of a cured product, the modulus of elasticity is excessively high. In addition, the molecular weight of the compound having two or more propylene groups in one molecule is preferably 500 or more and 50,000 or less, more preferably 500 or more and 5,000 or less, and particularly preferably 500 or more and 2,000 or less, as described above. If it is in this range, workability is good, and an adhesive layer having a low modulus of elasticity can be obtained. Such a polyether compound having two or more propylene groups in one molecule can be obtained by reacting a polyether polyol with (meth)acrylic acid with a derivative thereof.

The polyester is preferably an organic group having 3 to 6 carbon atoms which is repeated with an ester bond, and is preferably one which does not contain an aromatic ring. In the case of containing an aromatic ring, a compound having two or more propylene groups in one molecule becomes solid or highly viscous, and in the case of a cured product, the modulus of elasticity is excessively high. In addition, the molecular weight of the compound having two or more propylene groups in one molecule is preferably 500 or more and 50,000 or less, more preferably 500 or more and 5,000 or less, and particularly preferably 500 or more and 2,000 or less, as described above. If it is in this range, workability is good, and an adhesive layer having a low modulus of elasticity can be obtained. Such a polyester compound having two or more propylene groups in one molecule can be obtained by reacting a polyester polyol with (meth)acrylic acid with a derivative thereof.

The polycarbonate is preferably an organic group having a carbon number of 3 to 6 which is repeated with a carbonate bond, and is preferably one which does not contain an aromatic ring. In the case of containing an aromatic ring, a compound having two or more propylene groups in one molecule becomes solid or highly viscous, and in the case of a cured product, the modulus of elasticity is excessively high. In addition, the molecular weight of the compound having two or more propylene groups in one molecule is preferably 500 or more and 50,000 or less, more preferably 500 or more and 5,000 or less, and particularly preferably 500 or more and 2,000 or less, as described above. If it is in this range, workability is good, and an adhesive layer having a low modulus of elasticity can be obtained. Such a polycarbonate compound having two or more propylene groups in one molecule can be obtained by reacting a polycarbonate polyol and (meth)acrylic acid with a derivative thereof.

The poly(meth) acrylate is preferably a copolymer of (meth)acrylic acid and (meth) acrylate, a copolymer of a hydroxyl group (meth) acrylate and a (meth) acrylate having no polar group. And a copolymer of a glycidyl (meth) acrylate and a (meth) acrylate having no polar group. The molecular weight of the compound having two or more propylene groups in one molecule is preferably 500 or more and 50,000 or less, and more preferably 500 or more and 25,000 or less as described above. If it is in this range, workability is good, and an adhesive layer having a low modulus of elasticity can be obtained. Such a (meth) acrylate compound having two or more propylene groups in one molecule can be used in the case of a copolymer having a carboxyl group by a (meth) acrylate having a hydroxyl group or a glycidyl group ( Methyl) acrylate reaction can be obtained by reacting (meth)acrylic acid with a derivative thereof in the case of a copolymer having a hydroxyl group, and in the case of a copolymer having a glycidyl group, Methyl)acrylic acid is obtained by reacting with its derivative.

Polybutadiene can be obtained by reacting a polybutadiene having a carboxyl group with a (meth) acrylate having a hydroxyl group or a (meth) acrylate having a glycidyl group, or a polybutadiene having a hydroxyl group ( Methyl)acrylic acid and its derivatives are obtained by reaction, and can also be obtained by reacting polybutadiene obtained by adding hydroxy maleic anhydride with a hydroxyl group-containing (meth) acrylate.

Butadiene acrylonitrile copolymer can be obtained by copolymerizing a butadiene acrylonitrile copolymer having a carboxyl group with a (meth) acrylate having a hydroxyl group or a glycidyl group (A) Acrylate reaction to obtain.

The compound having two or more allyl groups in one molecule is preferably a polyether, a polyester, a polycarbonate, a polyacrylate, a polymethacrylate, a polybutadiene, a butyl having a molecular weight of 500 or more and 50,000 or less. A diene acrylonitrile copolymer having an allyl compound, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Dicarboxylic acids and derivatives thereof, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and derivatives thereof, and allyl alcohol A reaction product of a diallyl compound obtained by the reaction with a diol such as ethylene glycol, propylene glycol or butylene glycol.

The compound having two or more maleimide groups in one molecule is preferably, for example, N,N'-(4,4'-diphenylmethane) bismaleimide or bis ( 3-ethyl-5-methyl-4-maleimidoimine phenyl)methane, 2,2-bis[4-(4-maleoximine phenoxy)phenyl]propane And other bimaleimide compounds. More preferred are compounds obtained by the reaction of dimer acid diamine and maleic anhydride, and by maleic acid such as maleimide acetic acid or maleimide hexanoic acid. A compound obtained by the reaction of a hydrazinium amino acid with a polyol. The maleimide-imidized amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid, and is preferably a polyether polyol or a polyester polyol. The polycarbonate polyol, the polyacrylate polyol, and the polymethacrylate polyol preferably contain no aromatic ring. In the case of containing an aromatic ring, a compound having two or more maleimide groups in one molecule becomes solid or highly viscous, and in the case of a cured product, the modulus of elasticity becomes too high.

Moreover, in order to adjust various characteristics of the resin composition of this embodiment, it can also be used in the range which does not impair the effect of (A) thermosetting resin. The following compounds. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 3-hydroxybutyl methacrylate, 4-hydroxybutyl (meth) acrylate, mono (meth) acrylate, glycerol di(meth) acrylate, trimethylolpropane mono (meth) acrylate Ester, trimethylolpropane di(meth) acrylate, neopentyl alcohol mono (meth) acrylate, neopentyl alcohol di (meth) acrylate, neopentyl alcohol tri (meth) acrylate a hydroxyl group-containing (meth) acrylate such as neopentyl glycol mono(meth)acrylate, and a carboxyl group obtained by reacting such a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid or a derivative thereof (meth) acrylate and the like. Examples of the dicarboxylic acid which can be used herein include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and cis. Butylene diacid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and derivatives thereof.

In addition to the above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate can also be used. , isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (methyl) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, zinc single (A) Acrylate, zinc di(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, neopentyl glycol (meth)acrylate, Trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, Perfluorooctyl methacrylate, perfluorooctyl (meth) acrylate, ethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, 1,4-butanediol bis ( Methyl) acrylate, 1,6-hexanediol II (Meth) acrylate, 1,9-nonanediol di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate, 1,10-nonanediol di(meth)acrylic acid Ester, butanediol di(meth)acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy diethylene glycol (meth) acrylate Ester, N, N'-methylenebis(meth) acrylamide, N, N'-extended ethylene bis(methyl) acrylamide, 1,2-di(methyl) propylene decyl glycol , di(methyl)propenyloxymethyltricyclodecane, N-(methyl)propenyloxyethyl maleimide, N-(methyl)acryloxyethyl 6 Hydroquinoneimine, N-(meth)acrylomethoxyethyliminoimine, n-vinyl-2-pyrrolidone, styrene derivatives, α-methylstyrene derivatives, and the like.

Further, it is preferred to use a thermal radical polymerization initiator as a polymerization initiator of a resin having two or more radical polymerizable carbon-carbon double bonds in one molecule of (A) a thermosetting resin. The material to be used as the thermal radical polymerization initiator is not particularly limited, but it is preferably decomposed in a rapid heating test (1 g of the sample is placed on a hot plate at a decomposition start temperature at a temperature of 4 ° C/min). The temperature is 40 ° C or more and 140 ° C or less. When the decomposition temperature is less than 40 ° C, the storage stability of the resin composition at normal temperature is deteriorated, and if it exceeds 140 ° C, the curing time becomes extremely long and is not preferable.

Specific examples of the thermal radical polymerization initiator which satisfies this point include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoxyacetate, acetoxyacetone peroxide, 1, 1-bis(tertiary butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(tri-hexylperoxy)cyclohexane, 1,1-double (three-stage) Hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(tri-butylperoxy)cyclohexane, 2,2-bis(4,4-di-tris Butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, 4,4-bis(tri-butylperoxy)pentanoic acid n-butyl ester, 2 , 2-bis(tertiary butylperoxy)butane, 1,1-bis(tri-butylperoxy) 2-methylcyclohexane, tertiary butyl hydroperoxide, hydroperoxide, menthane, 1,1,3,3-tetramethylbutyl hydroperoxide, tertiary hexyl hydroperoxide, Dicumyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane, α,α'-bis(tri-butylperoxy)diisopropyl Base benzene, tertiary butyl cumene peroxide, di-tertiary butyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)-3-hexyne, Isobutyl fluorenyl peroxide, 3,5,5-trimethylhexyl peroxide, octyl octyl peroxide, dodecyl peroxide, peroxycinnamic acid, m-toluamyl peroxide, benzoyl peroxide , diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl peroxydicarbonate), di-3-methoxybutyl peroxydicarbonate, di-2-ethyl peroxydicarbonate Hexyl hexyl ester, di-secondary butyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate Ester) ester, α,α'-bis(xindecylperoxy)diisopropylbenzene, cumene peroxy neodecanoate, peroxy neodecanoic acid 1,1,3,3,-four Methyl butyl ester, peroxy neodecanoic acid 1-ring Base-1-methylethyl ester, tertiary hexyl peroxy neodecanoate, tertiary butyl peroxy neodecanoate, tertiary hexyl peroxyisobutyrate, tertiary butyl peroxyisobutyrate, 2 , 5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl oxy-2-ethylhexanoate, tertiary hexyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-2-ethylhexanoate, peroxidation Tert-butyl butyl butyrate, tertiary butyl maleate, butyl peroxydoteate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, Oxidation of isopropyl isopropyl carbonate, tertiary butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-bis(benzylidene peroxy)hexane, Oxidized acetic acid tert-butyl acrylate, benzoic acid tert- hexyl ester, meta-m- tolylmethyl benzoyl benzoate, butyl peroxybenzoate, bis (tertiary butylperoxy) Phthalate, tertiary butyl peroxypropylene carbonate, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl ketone Alternatively, they may be used singly or in combination of two or more types for suppressing sclerosing. Further, the above-mentioned resin having two or more radical polymerizable carbon-carbon double bonds in one molecule is also preferably used in combination with a cyanate resin, an epoxy resin, or a maleimide resin.

(A) The maleic imide resin of the thermosetting resin is a compound containing one or more maleimide groups in one molecule, and is formed by reacting a maleic acid imide group by heating. A 3 dimensional mesh structure to harden the compound. For example, N,N'-(4,4'-diphenylmethane) bismaleimide, bis(3-ethyl-5-methyl-4-methylenebuteneimide benzene) A bismaleimide resin such as a reaction product of methane or 2,2-bis[4-(4-maleoximeimidophenoxy)phenyl]propane. More preferably (A) a thermosetting resin maleimide resin is a compound obtained by reacting a dimer acid diamine with maleic anhydride, and by using maleimide A compound obtained by reacting a maleic acid imidized amino acid such as acetic acid or maleimide hexanoic acid with a polyhydric alcohol. The maleimide-imidized amino acid can be obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid, and the polyhydric alcohol is preferably a polyether polyol, a polyester polyol, or a polycarbonate. Ester polyols, poly(meth) acrylate polyols, especially those which do not contain an aromatic ring. The maleimide gene can be reacted with an allyl group and is also suitable for use with an allyl ester resin. The allyl ester resin is preferably an aliphatic one, and particularly preferably a compound obtained by transesterification of a diallyl cyclohexane adipate with an aliphatic polyol. Alternatively, it may be used in combination with a cyanate resin, an epoxy resin, or an acrylic resin.

(A) The amount of the thermosetting resin to be added is 2% by weight or more and 40% by weight or less, preferably 5% by weight or more and 35% by weight or less based on the total resin composition. Within this range, the workability and heat resistance of the resin composition can be made more excellent.

(metal particles)

(B) The metal particles are not particularly limited as long as the d ₉₅ is 10 μm or less. However, in order to make the conductivity and the thermal conductivity excellent, silver particles are preferable. In addition to silver, at least one of metal particles formed of copper, gold, nickel, palladium, aluminum, tin, zinc, or the like, or alloy particles of such metals may be used.

Here, the silver particles include metal particles in which the surface of the metal particles composed of copper, gold, nickel, palladium, aluminum, tin, zinc, or the like is coated with silver.

(B) The shape of the metal particles is not particularly limited, and is preferably a scaly shape or an elliptical spherical shape. When the shape of the metal particles is a scaly shape or an elliptical shape, the obtained adhesive layer is particularly excellent in thermal conductivity and electrical conductivity.

Further, (B) the particle diameter of the metal particles differs depending on the viscosity of the resin composition required, and the volume-based particle size distribution d ₅₀ of the volume-based particle size distribution measured by the flow field type particle image analyzer of the metal particles is preferably 0.5. The μm or more is 8 μm or less, and more preferably 0.6 μm or more and 6 μm or less. When the median diameter d _{50 is} less than 0.5 μm, the viscosity becomes high, and if the median diameter d ₅₀ exceeds 8 μm, the resin component tends to flow out and bleed out at the time of coating or hardening, which is less preferable. Further, when the median diameter d ₅₀ exceeds 8 μm, when the resin composition is applied by a dispenser, the outlet of the needle tube may be clogged and may not be used continuously for a long period of time. Further, the particle size distribution of the metal particles is preferably one peak (monomodality).

Further, in the metal particles (B) used, the content of the halogen impurities and the ionic impurities such as alkali metal ions is preferably 10 ppm or less. Further, the metal particles (B) used in the present embodiment may be those which have been treated with a decane coupling agent such as alkoxysilane, decyloxydecane, decane alkane or an organic amine decane.

Further, (B) metal particles with respect to 100 parts by weight of the entire resin composition The blending amount is preferably 50 parts by weight or more and 95 parts by weight or less, more preferably 60 parts by weight or more and 90 parts by weight or less. When it is in this range, good thermal conductivity and electrical conductivity are obtained, and workability is also excellent. When the (B) metal particles in the resin composition are less than 50 parts by weight, (B) the metal particles are covered with (A) a thermosetting resin, and (B) the metal particles may not be provided in parallel with the direction of gravity. When the viscosity of the resin composition is increased, the workability is lowered, and the cured product of the resin composition becomes brittle, which may lower the solder resistance and is less preferable.

(insulating particles)

Further, the resin composition of the present embodiment may further contain (C) insulating particles. (C) The insulating particles are not particularly limited, and examples thereof include an inorganic filler such as cerium oxide particles or alumina, and an organic filler such as an organic polymer.

(C) The insulating particles are preferably ones which can contain (B) metal particles, and in the case of semiconductor use, more preferably have the same particle diameter. Further, (C) the insulating particles are preferably used for imparting low thermal expansion property, low moisture absorption rate, and the like to the adhesive layer 1 of the present embodiment, and it is more preferable to keep the thickness of the adhesive layer 1 after curing.

Further, the (C) insulating particles are not particularly limited, but it is preferable that the volume-based particle size distribution measured by the flow field type particle image analyzer has a d ₉₅ of 10 μm or less. When the d ₉₅ of the (C) insulating particles contained in the resin composition is 10 μm or less, the (C) insulating particles and the (B) metal particles are more difficult to settle or aggregate, and the workability is further improved.

Further, (C) the particle size of the insulating particles differs depending on the viscosity of the resin composition required, and the median diameter d ₅₀ of the volume-based particle size distribution of the (C) insulating particles measured by a flow field type particle image analyzer is generally It is preferably 2 μm or more and 8 μm or less, more preferably 3 μm or more and 7 μm or less. In the case where the median diameter d _{50 is} less than 2 μm, the viscosity is high and it is not preferable. On the other hand, when the median diameter d ₅₀ is 2 μm or more, the (B) metal particles can be more efficiently arranged in such a manner that the long axis is parallel to the direction of gravity.

On the other hand, when the median diameter d ₅₀ exceeds 8 μm, it is less preferable because the resin component is likely to flow out and bleed out during coating or hardening. On the other hand, when the median diameter d ₅₀ is 8 μm or less, the (B) metal particles can be more efficiently arranged such that the long axis is parallel to the direction of gravity.

In addition, the amount of the (C) insulating particles is preferably 5 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the total resin composition, and in this range, good thermal conductivity and electrical conductivity are obtained, and workability is also excellent. When the (C) insulating particles in the resin composition are less than 5 parts by weight, the (B) metal particles may not be aligned with the direction of gravity and parallel, and if more than 30 parts by weight, the viscosity of the resin composition may be changed. When the workability is lowered and the cured product of the resin composition becomes brittle, the solder resistance may be lowered to be less preferable.

Specific examples of the inorganic filler include aluminum nitride, calcium carbonate, cerium oxide, and aluminum oxide. The inorganic filler is preferably one in which the column (B) metal particles are arranged, and in the case of use as a semiconductor, it is preferred that the particles have the same particle diameter. Further, if the inorganic filler can impart low thermal expansion property, low moisture absorption rate, etc. to the adhesive layer 1, it is more preferable to keep the thickness of the adhesive layer 1 constant. Among them, particularly preferred is cerium oxide or aluminum oxide.

Specific examples of the organic filler include styrene type, styrene/isoprene type, styrene/acrylate type, methyl methacrylate type, ethyl acrylate type, acrylic type, and ethyl methacrylate type. , acrylonitrile, methacrylate, divinylbenzene, n-butyl acrylate, nylon, oxime, amine ester, melamine, cellulose, acetamidine, polyglucamine Sugar, acrylate rubber / methacrylate, vinyl, ethylene / A polymer such as acrylic, polypropylene or benzoxazine, phenol, fluorine or vinylidene chloride.

The organic filler is preferably one which can be classified as (B) metal particles, and is preferably used in the case of semiconductor use. Further, it is more preferable that the organic filler imparts low thermal expansion property, low moisture absorption rate, and the like to the adhesive layer 1, and the thickness of the adhesive layer 1 is kept constant. Among them, a crosslinked organic polymer containing polymethyl methacrylate as a main component is particularly preferred.

The resin composition of the present embodiment preferably further contains a decane coupling agent such as an epoxy decane, a mercapto decane, an amino decane, an alkyl decane, a ureido quinane or a vinyl decane, or a titanate coupling agent or aluminum. A coupling agent such as a coupling agent or an aluminum/zirconium coupling agent.

In the resin composition of the present embodiment, other additives may be used as needed. Other additives include coloring agents such as carbon black; low-stress components such as eucalyptus oil and silicone rubber; inorganic ion exchangers such as hydrotalcite, antifoaming agents, surfactants, various polymerization inhibitors, and antioxidants; Additives are fine.

In addition, in the resin composition of the present embodiment, an organic compound can be added as needed within a range that does not affect the arrangement of the (B) metal particles when the cured product is used. For example, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,3-trimethyl Pentane, isooctane, decane, 2,2,5-trimethylhexane, decane, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, Ethylbenzene, cumene, 1,3,5-trimethylbenzene, butylbenzene, p-isopropylbenzene, diethylbenzene, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, Pentane, cyclohexene, α-pinene, dipentene, decahydronaphthalene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, three Butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tertiary pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1- Pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2- Ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol , 4-methylcyclohexanol, rosin alcohol, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, dipropyl Ether, diisopropyl ether, dibutyl ether, anisole, phenethyl ether, methoxytoluene, benzyl ethyl ether, 2-methylfuran, tetrahydrofuran, tetrahydropyran, 1,2-dimethyl Oxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, acetaldehyde, acetone, methyl ethyl ketone, 2-pentanone, 3-pentyl Ketone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetone acetonide, isopropylidene acetonide, phorone, cyclohexanone, methyl Cyclohexanone, propionic acid, butyric acid, isobutyric acid, trimethylacetic acid, valeric acid, isovaleric acid, 2-ethylbutyric acid, propionic anhydride Butyric anhydride, ethyl formate, propyl formate, butyl formate, isobutyl formate, formic acid, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, acetic acid Butyl butyl ester, amyl acetate, isoamyl acetate, 3-methoxybutyl acetate, secondary hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid cyclohexane Ester, methyl propionate, ethyl propionate, butyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, isobutyl isobutyrate , 2-hydroxy-2-methylpropionic acid ethyl ester, isovaleric acid ethyl, isoamyl isovalerate, benzoic acid methyl, diethyl oxalate, diethyl malonate, ethylene glycol Acetate, ethyl diacetate, monoacetin, diethyl carbonate, methyl nitrate, nitrate, 1-nitropropane, 2-nitropropane, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, pentane Nitrile, benzonitrile, diethylamine, triethylamine, dipropyl Amine, diisopropylamine, dibutylamine, diisobutylamine, aniline, N-methylaniline, N,N-dimethylaniline, pyrrole, piperidine, pyridine, α-methylpyridine, β-methylpyridine, γ -methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, 2-methoxymethanol, 2-ethoxymethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol , 2-butoxyethanol, 2-(pentyloxy)ethanol, decyl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2 -propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetone alcohol, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, morpholine, N-ethyl? Porphyrin, methyl lactate, ethyl lactate, butyl lactate, amyl lactate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, methyl acetate Ethyl acetate and the like. It is possible to use two or more types in combination, and it is not limited to the use of them.

The resin composition of the present embodiment can be produced, for example, by mixing each component and then kneading it under vacuum using three rolls.

The viscosity of the resin composition is preferably 1 Pa ‧ or more and 100 Pa ‧ or less. Whether it is lower or higher than it is not suitable because a good thickness of the adhesive layer cannot be obtained after coating. Here, the viscosity value was measured at 2.5 rpm at 25 ° C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., 3° cone). A better viscosity range is below 2 Pa‧s and above 90 Pa‧s, and more preferably below 2 Pa‧s and above 80 Pa‧s.

On the other hand, the viscosity change rate before and after the resin composition is placed at 25 ° C for 24 hours is preferably 100% or less. If the viscosity change rate exceeds 100% When the resin composition is applied to the substrate 2 or the semiconductor element 3, there is a problem that workability or thickness accuracy after coating may occur. While standing at 25 ° C for 24 hours, specifically, 5 g of the resin composition was placed on a glass plate, which was spread to a thickness of 100 μm with a spatula, and left at 25 ° C for 24 hours.

(semiconductor device)

Next, a semiconductor device produced by using a resin composition in the present embodiment will be described. Fig. 1 is a cross-sectional view showing the configuration of a semiconductor device 10 of the present embodiment.

In the present embodiment, the semiconductor device 10 includes a substrate 2, a semiconductor element 3, and an adhesive layer 1 interposed between the substrate 2 and the semiconductor element 3 to adhere the both.

The adhesive layer 1 is formed by applying the resin composition of the present embodiment to a semiconductor element or a substrate, and then crimping the semiconductor element 3 and the substrate 2.

The thickness of the adhesive layer 1 is not particularly limited, but is preferably 2 μm or more and 100 μm or less, and more preferably 2 μm or more and 30 μm or less. By being at least the lower limit value, the adhesion strength can be further exhibited. On the other hand, if it is at most the upper limit value, the conductivity and thermal conductivity can be further improved.

The base material 2 is not particularly limited, and examples thereof include a 42-aluminum lead frame, a lead frame such as a copper lead frame, a heat radiating member such as a heat sink and a heat sink, and a glass epoxy substrate (a substrate made of a glass fiber reinforced epoxy resin). An organic substrate such as a BT substrate (a substrate using a BT resin composed of a cyanate monomer and an oligomer thereof and bismaleimide), another semiconductor element, a semiconductor wafer, a spacer, or the like. Among these, a lead frame, a heat sink or an organic substrate which can further effectively exhibit the conductivity and thermal conductivity of the adhesive layer 1 is preferable. Furthermore, the organic substrate is preferably a BGA (Ball Grid Array) substrate.

The semiconductor element 3 is electrically connected to the lead 4 through the pad 7 and the bonding wire 6 . On the other hand, the semiconductor element 3 is sealed by a sealing material layer 5 around it.

In the case of the conventional resin composition, particularly in the case of a semiconductor element having a small adhesive wafer width, it is difficult to apply an appropriate amount of the resin composition, and the resin composition may overflow from the semiconductor element.

The resin composition of the present embodiment is suitable for adhering a semiconductor element having a small wafer width because of a small change in viscosity and excellent workability. Therefore, the semiconductor element 3 is not particularly limited, but is preferably a semiconductor element having a wafer width of 2 μm or less, such as a light-emitting diode element or a semiconductor laser element.

(Method of manufacturing a semiconductor device using a resin composition)

The method for producing the semiconductor device 10 using the resin composition in the present embodiment is not particularly limited, and a well-known method can be used. For example, after a resin bond is applied or embossed to a specific portion of the substrate 2 using a commercially available die bonder, the substrate 2 and the semiconductor element 3 are crimped, and then heat-hardened to form an adhesive layer 1 .

Then, wire bonding is performed, and the sealing device layer 5 is formed by using an epoxy resin to fabricate the semiconductor device 10. Alternatively, a flip-chip BGA (ball gate array) sealed with an underfill material after flip chip bonding may be used, and the resin composition may be applied or embossed on the inner surface of the semiconductor wafer, and a heat-dissipating component such as a heat sink or a lead may be mounted. Heat hardening and other methods.

Here, the point is that after the resin composition is filled in the cylinder of the die bonder, the resin composition is quantitatively discharged onto the substrate 2 or the semiconductor element by extruding the resin composition by a piston or by air pressure or the like. A method of coating a specific position (adhesive surface) of at least one of the surfaces of the three.

The embossing means pressing the front end of the transfer pin to the resin composition, and moving the front end of the transfer pin to which the resin composition is attached to the surface of at least one of the substrate 2 or the semiconductor element 3. Immediately above a specific position, via adhesion of at least one of the substrate 2 or the semiconductor element 3 to the transfer pin A method of coating a resin composition on the surface.

Further, in the case of bonding a semiconductor element having a wafer width of 2 μm or less, it is preferable to apply a resin composition by spotting or imprinting with a very thin needle tube. In the present embodiment, the resin composition has a small change in viscosity and excellent workability, and a small amount of the resin composition can be applied to the substrate with a precise thickness by spotting or imprinting of the ultrafine needle tube.

[Examples]

Specific embodiments of the present embodiment are shown below, but are not limited thereto. In the present embodiment, the following components were used for each component of the resin composition.

Thermosetting resin

Epoxy Resin A: Bisphenol F-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-303S)

Epoxy resin B: m-p-cresol glycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., CGE, epoxy equivalent 165)

Acrylic resin A (acrylate A): diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER 4EG)

Acrylic resin B (acrylate B): hydroxy group-containing acrylate (CHDMMA, manufactured by Nippon Kasei Co., Ltd.)

Acrylic resin C (acrylate C): acrylate containing carboxyl group (LIGHT ESTER HOMS, manufactured by Kyoeisha Chemical Co., Ltd.)

Acrylic resin D (Acrylate D): Triacrylate (LIGHT ESTER TMP, manufactured by Kyoeisha Chemical Co., Ltd.)

Maleimide resin (m-butylene imine compound): maleimide compound (manufactured by Dainippon Ink and Chemicals, MIA-200)

Allyl ester resin (allyl ester compound): allyl ester compound (DA101, manufactured by Showa Denko)

2. Additives

Hardener A (epoxy hardener A): bisphenol F (manufactured by Dainippon Ink and Chemicals, BPF, hydroxyl equivalent 100)

Hardener B (epoxy hardener B): dicyandiamide (DDA, manufactured by ADEKA)

Hardening Catalyst (Epoxy Catalyst A): 2-Phenyl-4-methyl-5-hydroxymethylimidazole (CURESOL 2P4MHZ, manufactured by Shikoku Chemical Industries, Ltd.)

Coupler A: Epoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E)

Coupler B: bis(trimethoxydecylpropyl) tetrasulfide (manufactured by DAISO, CABRUS 4)

Coupling agent C: Vinyl decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503P)

Polymerization initiator (peroxide): peroxide (chemical compound AKZO, Perkadox BC)

3. Metal particles

Flaky silver particle A (flaky silver powder A): (Fukuda Metal Foil Powder Co., Ltd., Agc-TC6, d ₅₀ : 14.0 μm, d ₉₅ : 23.0 μm, 10 μm < 13%)

Scale-like silver particles B (flaky silver powder B): (Ferro, SF-78, d ₅₀ : 9.5 μm, d ₉₅ : 14.0 μm, 10 μm < 54%)

Scale-like silver particles C (flaky silver powder C): (Ferro, SF-65, d ₅₀ : 4.0 μm, d ₉₅ : 13.0 μm, 10 μm < 12%)

Scale-like silver particles D (flaky silver powder D): (Fukuda Metal Foil Powder Co., Ltd., Agc-2611, d ₅₀ : 3.7 μm, d ₉₅ : 8.5 μm, 10 μm < 5%)

Scale-like silver particles E (flaky silver powder E): (manufactured by DOWA ELECTRONICS, FA-S-6, d ₅₀ : 2.2 μm, d ₉₅ : 6.0 μm, 10 μm < 0%)

Spherical silver particle A (spherical silver powder A): (manufactured by DOWA ELECTRONICS, AG2-1C, d ₅₀ : 1.7 μm, d ₉₅ : 3.6 μm, 10 μm < 0%)

4. Insulating particles

Crosslinked PMMA-1: (Art-pearl GR-800, 10μm<7%)

Crosslinked PMMA-2: (Art-pearl SE-006T, 10μm<4%)

Crosslinked PMMA-3: (Art-pearl J-7P, 10μm<0%)

Here, X of 10 μm < X% means a volume ratio of metal particles or insulating particles having a particle diameter of more than 10 μm.

The particle size was measured using the flow field type particle image analyzer FPIA-3000 manufactured by HOSOKAWA MICRON Co., Ltd. under the following conditions.

Measurement mode: HPF

Quantitative counting

Objective lens: 20 times

Optical system: bright field of view

Temperature: room temperature

Pressure: 0.22MPa

[Examples 1 to 13 and Comparative Examples 1 to 3]

The above components were blended in the proportions shown in Table 1, and the resin composition was separately prepared by kneading in a vacuum chamber at 2 mmHg for 15 minutes by kneading using three rolls. The blending ratio is parts by weight.

(evaluation test)

The following evaluation tests were carried out on the resin compositions obtained above. The evaluation results are shown in Table 1.

(viscosity)

After the preparation of the above resin composition, the value measured at 2.5 rpm at 25 ° C using an E-type viscometer (3 ° cone) was used. Then, after the prepared resin composition was allowed to stand at 25 ° C for 24 hours, it was also measured at 25 ° C and 2.5 rpm. The value is determined, and the viscosity change rate after 24 hours is calculated by the following formula (1). Further, it was allowed to stand at 25 ° C for 24 hours. Specifically, 5 g of the resin composition was placed on a glass plate, stretched to a thickness of 100 μm with a spatula, and left at 25 ° C for 24 hours.

Viscosity change rate after standing for 24 hours [%] = 100 × (viscosity after standing for 24 hours - current viscosity after production) / (current viscosity after production) (1)

(spit sex)

An extremely fine needle having a nozzle diameter of 100 μm and a dispenser were used to evaluate the workability when the resin composition was discharged. Each symbol is as follows.

OK: The discharge rate and application of the resin composition are no problem.

NG: The resin composition could not be discharged.

As is clear from Table 1, the resin compositions of Examples 1 to 13 have a small change rate of viscosity, good discharge property, and excellent workability. Further, these resin compositions are also excellent in workability when the semiconductor element having a wafer width of 2 μm or less is subjected to die adhesion.

[Industry Utilization]

According to the present invention, since the resin composition excellent in workability can be provided, the present invention is extremely useful industrially.

1‧‧‧Adhesive layer

2‧‧‧Substrate

3‧‧‧Semiconductor components

4‧‧‧ pin

5‧‧‧Sealing material layer

6‧‧‧bonding leads

7‧‧‧ pads

10‧‧‧Semiconductor device

Fig. 1 is a cross-sectional view showing the configuration of a semiconductor device of the embodiment.

Claims (13)

A resin composition for adhering a paste-like resin composition of a semiconductor element and a substrate, comprising: a thermosetting resin; metal particles; and insulating particles; wherein the metal particles are subjected to flow field type particle image analysis The volume-based particle size distribution measured by the flow particle image analyzer is d ₉₅ based on 10 μm or less; the volume-based particle size distribution of the metal particles measured by the flow field type particle image analyzer is ₅₀ μm 0.5 μm. 8 μm or less; the insulating particles are one or more selected from the group consisting of cerium oxide particles, alumina, and an organic polymer; and the amount of the insulating particles is 12 to 30 parts by weight based on 100 parts by weight of the entire resin composition; The volume-based particle size distribution measured by the flow field type particle image analyzer of the particles is d ₉₅ based on 10 μm or less. The resin composition of the first aspect of the patent application has a viscosity change rate of 100% or less after standing at 25 ° C for 24 hours. The resin composition of claim 1 or 2, wherein the metal particles comprise silver particles. The resin composition according to claim 1 or 2, wherein the thermosetting resin comprises an epoxy resin. The resin composition of claim 1 or 2, wherein the resin composition is used for imprinting, which transfers the resin composition to the semiconductor element and the aforementioned base by a transfer pin At least one of the materials Adhesive surface. The resin composition according to claim 1 or 2, wherein the thermosetting resin comprises an epoxy resin and a curing accelerator; and the curing accelerator is an imidazole compound having a melting point of 180 ° C or higher. The resin composition according to claim 1 or 2, wherein the thermosetting resin comprises a resin having two or more radical polymerizable carbon-carbon double bonds in one molecule, and a polymerization initiator; In the rapid heating test, 1 g of the sample was placed on a hot plate, and the decomposition temperature in the decomposition starting temperature at a temperature of 4 ° C /min was a thermal radical polymerization initiator of 40 ° C or more and 140 ° C or less. A semiconductor device comprising: a substrate; a semiconductor element; and an adhesive layer sandwiched between the substrate and the semiconductor element for adhering the two; wherein the adhesive layer is used as in claim 1 or The resin composition of the two items is formed. The semiconductor device of claim 8, wherein the semiconductor element has a wafer width of 2 μm or less. The semiconductor device of claim 8, wherein the semiconductor element is a light emitting diode element or a semiconductor laser element. The semiconductor device of claim 8, wherein the substrate is a lead frame, a heat sink or a ball grid array (BGA) substrate. A method of manufacturing a semiconductor device according to the eighth aspect of the invention, comprising: coating a resin composition on at least one of a semiconductor element or a substrate a step of adhering the surface; and crimping the semiconductor element and the substrate, and heating and hardening to form an adhesive layer. The method of manufacturing a semiconductor device according to claim 12, wherein the step of applying the resin composition comprises: transferring the transfer resin to imprint the resin composition, or arranging the resin composition with a very thin needle tube.